Phosphorus containing sulfur compounds and method of using same



United States Patent 3,144,384 PHOSPHORUS C(DNTAINING SULFUR COM- POUNDSAND METHQD 0F USING SAME Paul C. Aichenegg, Prairie Village, Kans,assignor to Chemagro Corporation, New York, N.Y., a corporation of NewYork No Drawing. Filed Jan. 26, 1962, Ser. No. 169,088

22 Claims. (Cl. 167-22) This invention relates to novel phosphoruscontaining disulfides and their use as pesticides.

It is an object of the present invention to prepare novel phosphoryldisulfides.

Another object is to prepare novel thiophosphoryl disulfides.

An additional object is to prepare improved compositions and to developnew processes for killing nematodes.

A further object is to prepare improved compositions and to develop newprocesses for killing fungi.

Yet another object is to prepare improved compositions and to developnew processes for killing insects.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven herinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has been found that these objects can be attained by preparingcompounds having the formulae (I) (II) where R is selected from thegroup consisting of lower alkyl, phenyl, lower alkylphenyl, chlorophenyland bromophenyl, Y Y and Y are selected from the group consisting ofhydrogen, chlorine and bromine, at least two of them being a halogen ofatomic weight 35 to 80,

Y; is chlorine or bromine, and X is a chalcogen of atomic Weight between16 and 32, Le, it is oxygen or sulfur.

The compounds of Formula I have superior pesticidal properties to thecompounds of Formula II.

The compounds where R is lower alkyl, and partieu-0,0-dimethy1-phosphoryl-(2,2,2-trichloroethyl) disulfide;

0,0-dime'thyl-phosphoryl- 1,2,2,2-tetrachloroethyl) disulfide;

0,0-dimethyl-thiophosphoryl-(1,2-dibromovinyl) disulfide;

0,0-dimethyl-thiophosphoryl-(2,2-dibromovinyl) disulfide;

0,0-dimethyl-thiophosphoryll-chloro-Z-bromovinyl) disulfide;

0,0-dimethyl-thiophosphoryl- 1,2,2-tribromoethyl) disulfide;

0,0-dimethyl-thiophosphoryl- 1 ,2,2-tribromovinyl) disulfide;

0,0-dimethyl-thiophosphoryl-(l,2,2,2-tetrabromoethyl) disulfide;

0,0-dirnethyl-phosphoryl-(1,2-dibromovinyl) disulfide;

0,0-dimethyl-phosphoryl-(2,2-dbromoviny1) disulfide;

0,0-dime'thyl-ph0sphoryl- 1,2,2-tribromoethyl) disulfide0,0-diethyl-thiophosphoryl-(2,2-dichlorovinyl) disulfide;

0,0-diethyl-thiophosphoryl- 1,2-dichlorovinyl) disulfide0,0-diethyl-thiophosphoryl-(1,2,2-trichlorovinyl) disulfide;

0,0-diethyl-thiophosphoryl-(2,2,2-trichloroethyl) disulfide;

0,0-diethylthiophosphoryl-( 1,2,2,2-tetrachloroethyl) disulfide;

0,0-diethyl-phosphoryl-(2,2-dichlorovinyl) disulfide;

0,0-diethyl-phosphory1-(1,2-dichlorovinyl) disulfide;

0,0-diethyl-phosphory1-(1,2,2-trichlorovinyl) disulfide;

0,0-diethyl-phosphoryl-( 1,2,2-trichloroethyl) disulfide;

0,0-diethyl-phosphoryl-(2,2,2-trichloroethy1) disulfide;

0,0-diethyl-phosphoryl-(1,2,2,2-tetrach1oroethyl) disulfide;

0,0-diethyl-thiophosphoryl-(1,2-dibromovinyl) disulfide;

0,0-diethyl-thiophosphoryl-(2,2-dibromovinyl) disulfide;

0,0-diethyl-thiophosphoryll-bromo-Z-chlorovinyl) disulfide;

0,0-diethyl-thiophosphoryl- 1,2,2-tribromoethyl) disulfide;

0,0-diethyl-thiophosphoryl-(2,2,2-tribromoe'thyl) disulfide;

0,0-diethyl-phosphoryl-(1,2-dihromovinyl) disulfide0,0-diethyl-phosphoryl-(2,2-dibromovinyl) disulfide;

0,0-diethyl-phosphoryl-( 1,2,2-tribromovinyl) disulfide;

0,0-diethy1-phosphoryl- 1,2,2-tribromoethyl) disulfide;

O-methyl-O-ethyl-'th iophosphoryl-( 1,2-dichlorovinyl) disulfide;

O-inethyl-O-ethyl-phosphoryl-(2,2-dichlorovinyl) disulfide;

0,0-dipropyl-thiophosphoryl- 1,2-diehlorovinyl) disulfide;

0,0-dipropyl-thiophosphoryl-(2,2-dich1oroviny1) disulfide;

0,0-dipropyl-thiophosphoryl- 1,2,2-trichlorovinyl) disulfide;

0,0-dipropyl-thiophosphoryl-( 1,2,2-trichloroethyl) disulfide;0,0-dipropy1-phosphoryl-(1,2-dichlorovinyl) disulfide;0,0-dipropy1-phosphoryl-(2,2-dichlorovinyl) disulfide;0,0-dipropyl-phosphoryl- 1,2,2-trichlorovinyl) disulfide;0,0-dipropyl-phosphoryl-(2,2,2-trichloroethyl) disulfide;0,0-dipropyl-thiophosphoryl- 1,2-dibromovinyl) disulfide;0,0-dipr0py1-phosphoryl-(2,2-dibromovinyl) disulfide;0,0-diisopropyl-thiophosphoryl-(2,2-dich1orovinyl) disulfide;0,0-diisopropyl-thiophosphoryl- 1,2-diehlorovinyl) disulfide;

Patented Aug. 11, 1964 3 0,0-diisopropyl-phosphoryl-(2,2 dichlorovinyl)disulfide; 0,0-diisopropyl-thiophosphoryl-(1,2,2-trichlorovinyl)disulfide; 0,0-diispr0pyl-phosphoryl-(1,2,2-trichloroethyl) disulfide;

0,0-dibutyl-thiophosphoryl-(1,2-dichlorovinyl) disulfide;

0,0-dibutyl-thiophosphoryl- (2,2-dichlorovinyl) disulfide0,0-dibutyl-thiophosphoryl-(1,2,2-trichlorovinyl) disulfide;

0,0-dibutyl-thiophosphoryl-(2,2,2 trichloroethyl) disulfide;

0,0-dibutyl-phosphoryl-(1,2-dichlorovinyl) disulfide;

0,0-dibutyl-phosphoryl-(2,2-dichlorovinyl) disulfide;

0,0-dibutyl-phosphoryl-(1,2,2-trichlorovinyl) disulfide;

0,0-dibutyl-thiophosphoryl-(1,2-dibromovinyl) disulfide;

0,0-dibutyl-phosphoryl-(2,2-dibromovinyl) disulfide;

0,0-di secondary butyl-thiophosphoryl-(1,2-dichlorovinyl) disulfide;

0,0-di tertiary butyl-thiophosphoryl-(2,2-dichlorovinyl) disulfide;

0,0-di tertiary butyl-phosphoryl-(1,2-dichlorovinyl) disulfide;

0,0-diphenyl-thiophosphoryl-(1,2-dichlorovinyl) disulfide;

0,0-diphenyl-thiophosphoryl-(2,2-dichlorovinyl) disulfide;

0,0-diphenyl-thiophosphoryl- 1,2,2-trichloroviny1) disulfide;

0,0-diphenyl-thiophosphoryl-(1,2,2-trichloroethyl) disulfide;

0,0-diphenyl-phosphoryl-(1,2-dichlorovinyl) disulfide;

0,0-diphenyl-phosphoryl-(2,2-dichlorovinyl) disulfide;

0,0-diphenyl-phosphoryl-(perchlorovinyl) disulfide;

0,0-diphenyl-phosphoryl-(2,2,2-trichloroethyl) disulfide;

0,0-diphenyl-phosphoryl-(1,2-dibromovinyl) disulfide;

0,0-diphenyl-thiophosphoryl-(2,2-dibromovinyl) disulfide;

0,0-di-p-tolyl-thiophosphoryl-(1,2-dichlorovinyl) di sulfide;

0,0-di-o-tolyl-phosphoryl-(2,2-dich1orovinyl) disulfide;

0,0-di-m-tolyl-thiophosphoryl-(1,2,2-trichlorovinyl) disulfide;

0,0-di-p-chlorophenyl-thiophosphoryl-(1,2-dichlorovinyl) disulfide;

0,0-di-m-bromophenyl-phosphoryll ,-bromo-2-chlorovinyl disulfide.

The compounds of the present invention can be made by reacting theappropriate 0,0-dialkyl (or phenyl, or lower alkylphenyl or halophenyl)dithiophosphoric acid or alkali salt thereof or the appropriate0,0-dialkyl (or phenyl or lower alkylphenyl or halophenyl) thiophosphatewith the appropriate polyhalovinyl sulfenyl chloride or polyhaloethylsulfenyl chloride.

1,2-dichlorovinyl sulfenyl chloride, 2,2-dichlorovinyl sulfenylchloride, 1,2,2-trichlorovinyl sulfenyl chloride, 1,2-dibromovinylsulfenyl chloride, 1-chloro-2-bromovinyl sulfenyl chloride,

include 23. 1,2,2-trichloroethyl sulfenyl chloride, 2,2,2-trichloroethylsulfenyl chloride, 1,2,2,2-tetrachloroethyl sulfenyl chloride and1,2,2-tribromoethyl sulfenyl chloride.

The polyhalovinyl compounds of the present invention can also beprepared by dehydrohalogenating the corresponding 1,2,2- or2,2,2-trihaloethyl or l,2,2,2- tetrahaloethyl compounds. Also, theappropriate phosphoryl thiosulfenyl chloride can be added to monochloroacetylene or to dichloroacetylene. The adduct formed fromdichloroethylene can then be dehydrohalogenated in the event thepolyhalovinyl compounds are to be prepared. Also, the appropriate diortrialkyl phosphite can be reacted with the appropriate polyhalovinylthiosulfenyl chloride.

The general procedure employed in Examples 1-10 (unless otherwise notedin the example) for preparing the compounds of the present invention wasas follows:

1 part (a 510% excess) of the 0,0-dialkyl (or diphenyl) dithiophosphoricacid or the sodium 0,0-dialkyl thiolphosphate in 3 to 4 parts of aninert solvent or dispersing agent (chloroform and carbon tetrachloridebeing preferred) was reacted with aid of stirring and cooling at 5-10"C. with the indicated dichlorovinyl sulfenyl chloride or perchlrovinylsulfenyl chloride or trichloroethyl sulfenyl chloride. The sulfenylchloride was added dropwise.

In all cases in which the free acids were employed the reactions werecarried out under a vacuum of 200 250 mm. Hg in order to reduce theconcentration of anhydrous HCl in the reaction mixture. When the sodiumsalt of the acid was employed, the reaction was carried out atatmospheric pressure. In Examples 1, 2, 5, 6, 8, 9 and 10, as indicated,the 0,0-dimethyl and 0,0-diethyl dithiophosphoric acids were of purity.The 10% impurity was highly water soluble and inert and was removedunchanged prior to the vacuum stripping.

The sulfenyl chloride was added at the rate of about one drop per twoseconds or adjusted so as to maintain a colorless or faintly yellowsolution if such rate did not give this color condition. The reactionwas practically instantaneous and was easily visible by the rapiddecoloration of each drop of the red sulfenyl chloride solution. Thetotal reaction time for the quantities employed was about 10 minutes.

After standing for approximately one hour, the reaction mixtures werewashed with cooling with dilute sodium bicarbonate solution to removeresidual free HCl and unreacted thio or dithiophosphate, dried over anhydrous magnesium sulfate and stripped in high vacuum (less than 1 mm.)to remove all traces of solvent. In all cases in which the alkali saltsof the thiophosphates were used a simple water wash was sufficient todissolve the formed alkali chloride and remove excessive alkalithiophosphate.

The 2,2-dichlorovinyl phosphoryl disulfides could easily be distilled,whereas noticeable decomposition was observed on distillation of the1,2-dichlorovinyl phosphoryl disulfides.

Unless otherwise indicated, all parts and percentages are by weight.

EXAMPLE 1 11.8 grams of 90% free acid containing 0,0-dimethyldithiophosphoric acid (0.067 mol of free acid) dissolved in 30 ml. ofdry carbon tetrachloride were reacted in the manner described above with10 grams (0.0612 mol) of 2,2-dichloroviny1 sulfenyl chloride to give17.4 grams (99.8% yield) of crude 0,0-dimethyl-thiophosphoryl-(2,2-dichlorovinyl) disulfide as a bright yellow oil, 12 1.6032. Thepure disulfide obtained distilled at 103-105 C. at 0.017 mm. and had 111.6046, (1 1.475, Cl 25.6% (theory 24.9%), P 9.98% (theory 10.8%).

When 10.6 grams of pure 0,0-dimethyl dithiophosphoric acid was used inplace of the 11.8 grams of 90% free acid containing material, theresulting product obtained was the identical0,0-dimethyl-thiophosphoryl- (2,2-dichlorovinyl) disulfide.

EXAMPLE 2 13.0 grams of 90% free acid containing 0,0-diethyldithiophosphoric acid (0.063 mol) when dissolved in 50 ml. of dry carbontetrachloride and reacted as described in Example 1 with grams (0.0612mol) of 2,2-dichlorovinyl sulfenyl chloride gave 18.0 grams (94% yield)of crude 0,0-diethy1 thiophosphoryl-(2,2-dichlorovinyl) disulfide as abright yellow oil, 11 1.5747. The pure product had a B.P. 106-109" C.,r1 1.5760, 1 1.367, Cl 24.0% (theory 22.7%), P 8.52% (theory 9.9%), S28.8% (theory 30.7%).

EXAMPLE 3 17.8 grams (0.063 mol) of diphenyl dithiophosphoric acid weresuspended in 50 ml. of dry carbon tetrachloride and reacted as describedin Example 1 with 10 grams (0.0612 mol) of 2,2-dichlorovinyl sulfenylchloride to give 23 grams (92% yield) of crude 0,0-diphenylthiophosphoryl-(2,2-dichlorovinyl) disulfide as a heavy, deep yellow oilwhich decomposed on attempted distillation in high vacuum. The producthad 11 1.6421, d 1.404, C1 17.4% (theory 17.35%), P 6.74% (theory7.57%), S 24.1% (theory 23.45%).

EXAMPLE 5 11.8 grams of 90% pure 0,0-dimethyl dithiophosphoric acid(0.067 mol based on the content of free acid) were diluted with 30 ml.of dry carbon tetrachloride and reacted as described above with 10 grams(0.0612 mol) of 1,2-dichlorovinyl sulfenyl chloride to give 17.0 grams(97.5% yield) of crude 0,0-dimethyl thiophosphoryl- (1,2-dichlorovinyl)disulfide as a yellow oil, 11 1.6021. Noticeable decomposition wasobserved on distillation in vacuum. However, the pure material appearedto boil at 125-130 C. at 0.1 mm. Hg. It had an 21 1.6014, d 1.492, Cl25.5% (theory 24.9%), P 9.8% (theory 10.8%), S 33.4% (theory 33.7%).

EXAMPLE 6 13 grams of 90% pure 0,0-diethyl dithiophosphoric acid (0.063mol based on the free acid content) were suspended in 50 ml. of drycarbon tetrachloride and reacted as described in Example 5 with 10 grams(0.0612 mol) of 1,2-dichlorovinyl sulfenyl chloride to give 18.5 grams(94.5% yield) of crude 0,0-diethyl thiophosphoryl-(1,2- dichlorovinyl)disulfide as a yellow oil, n 1.5750. Distillation in high vacuumproceeded with some decomposition. The pure product had a boiling pointof 130-135" C. at 0.08 mm. The distillate had 11 1.5752, r1 1.382, Cl24.6% (theory 22.6%), P 8.55% (theory 9.9%), S 29.8% (theory 30.7%).

EXAMPLE 7 12.0 grams (0.0624 mol) of sodium 0,0-diethyl thiolphosphatewere suspended in 50 ml. of dry chloroform and reacted in the abovedescribed fashion with 10 grams (0.0612 mol) of 1,2-dich1orovinylsulfenyl chloride to give 17.0 grams (89.5% yield) of crude 0,0-diethylphosphoryl-(1,2-dichlorovinyl) disulfide as a brown oil, 11

1.5370. Distillation proceeded with decomposition. The approximateboiling point was ISO-135 C. at 0.07 mm. The distillate had an 111.5409, (1 1.395, Cl 24.9% (theory 23.9%), P 8.98% (theory 10.4%), S22.1% (theory 21.6%

EXAMPLE 8 16.0 grams of pure 0,0-diethyl dithiophosphoric acid (0.079mol based on the free acid content) were diluted with 50 ml. of drycarbon tetrachloride and reacted in the above described manner with 15.0grams (0.075 mol) of fresh perchlorovinyl sulfenyl chloride to give 24.5grams (94.8% yield) of crude0,0-diethyl-thiophospl1oryl-(1,2,2-trichlorovinyl) disulfide as a brightyellow oil, 11 1.5850. The pure product had a B.P. 112114 C. (with somedecomposition), 11 1.5893, d 1.4456, Cl 30.3% (theory 30.6%), S 27.4%(theory 27.6%), P 8.2% (theory 8.9%).

EXAMPLE 9 16.0 grams of 90% pure 0,0-diethyl dithiophosphoric acid(0.079 mol based on the free acid content) were diluted with 50 ml. ofdry carbon tetrachloride and reacted in the above described manner with15 grams (0.075 mol) of 1,2,2-trichloroethyl sulfenyl chloride to give24.5 grams (93.5% yield) of crude0,0-diethyl-thiophosph0ryl-(1,2,2-trichloroethyl) disulfide as an almostcolorless oil, r2 1.5636. The pure'product distilled at 124 126 C., at0.022 mm. Hg as a faintly yellow oil, 21 1.5665, d 1.4235, Cl 30.4%(theory 30.4%), S 27.0% (theory 27.48%), P 8.2% (theory 8.86%).

EXAMPLE 10 16.0 grams of 90% pure 0,0-diethy1 dithiophosphoric acid(0.079 mol based on the free acid content) were diluted with 50 ml. ofdry carbon tetrachloride and reacted in the above described manner with15 grams (0.075 mol) of 2,2,2-trichloroethyl sulfenyl chloride to give24.4 grams (93% yield) of crude0,0-diethyl-thioph0sphoryl-(2,2,2-trichloroethyl) disulfide as acolorless oil, 11 1.5592. The pure product had a B.P. M2 124 C., n1.5608, r1 1.4081, Cl 30.8% (theory 30.4%), S 27.4% (theory 27.48%), P8.0% (theory 8.86%).

EXAMPLE 11 9.7 grams (0.0277 mol) of the crude0,0-diethyl-thiophosphoryl (2,2,2-trichloroethy1) disulfide prepared inExample 10 were diluted with 50 ml. of dry benzene, warmed on a waterbath to 5055 C. and reacted by dropwise addition under stirring of atotal of 2.8 grams (a slight excess) of triethyl amine. Thedehydrochlorination was completed by keeping the reactant mixture at 60C. for a further 30 minutes. The product in the benzene was then Washedwith water, dilute hydrochloric acid and dilute sodium bicarbonate. Thebenzene solution was dried over anhydrous magnesium sulfate and highvacuum stripped to give 8.0 grams (92.5%) of crude0,0-diethyl-thiophosphoryl-(2,2-dichlorovinyl) disulfide as a reddishoil n 1.5813. Distillation in high vacuum furnished the pure productwhich had similar properties to that of the pure product of Example 2.

The compounds of the present invention can be used alone as nematocides,fungicides, insecticides (e.g., against two spotted mites, roaches andmilk weed bug), bactericides, but it has been found desirable to applythem to the pest, e.g., to the soil habitat of nematodes, together withinert'solids to form dusts or, more preferably, suspended in a suitableliquid diluent, preferably water. There can also be added surface activeagents or Wetting agents and inert solids in such liquid formulations.Desirably, 0.25-l% by weight of surface active or wetting agent isemployed. The active ingredient can be from 0.01 to by weight of theentire composition in such case.

In place of water there can be employed organic solvents as carriers,e.g., hydrocarbons such as benzene, toluene, Xylene, kerosene, dieseloil, fuel oil, and petroleum naptha, ketones such as acetone, methylethyl ketone and cyclohexanone, chlorinated hydrocarbons such as carbontetrachloride, chloroform, trichloroethylene and perchloroethylene,esters such as ethyl acetate, amyl acetate and butyl acetate, ethers,e.g., ethylene glycol monomethyl ether and diethylene glycol monomethylether, alcohols, e.g., ethanol, methanol, isopropanol, amyl alcohol,ethylene glycol, propylene glycol, and glycerine. Mixtures of water andorganic solvents, either as solutions or emulsions, can be employed.

The novel pesticides can also be applied as aerosols, e.g., bydispersing them in air by means of a compressed gas such asdichlorodifiuoromethane or trichlorofiuoromethane and other Freons, forexample.

The pesticides of the present invention can also be applied withnematocidal, fungicidal, bactericidal and insecticidal adjuvants orcarriers such as talc, pyrophyllite, synthetic fine silica, attapulgusclay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate,bentonite, fullers earth, cottonseed hulls, wheat flour, soybean flour,pumice, tripoli, wood flour, walnut shell flour, redwood flour andlignin.

It is frequently desirable to incorporate a surface active agent in thepesticidal compositions of the present invention. Such surface active orwetting agents are advantageously employed in both the solid and liquidcompositions. The surface active agent can be anionic, cationic ornonionic in character.

Typical classes of surface active agents include alkyl sulfonate salts,alkylaryl sulfonate salts, alkyl sulfate salts, alkylamide sulfonatesalts, alkylaryl polyether alcohols, fatty acid esters of polyhydricalcohols and the alkylene oxide addition products of such esters, andaddition products of long chain mercaptans and alkylene oxides. Typicalexamples of such surface active agents include the sodium alkylbenzenesulfonates having to 18 carbon atoms in the alkyl group, alkylphenolethylene oxide condensation products, e.g., p-isooctylphenol condensedwith 10 ethylene oxide units, soaps, e.g., sodium stearate and potassiumoleate, sodium salt of propynaphthalene sulfonic acid, (di-Z-ethylhexyl)ester of sodium sulfosuccinic acid, sodium lauryl sulfate, sodium saltof the sulfonated monoglyceride of cocoanut fatty acids, sorbitansesquioleate, lauryl trimethyl ammonium chloride, octadecyl trimethylammonium chloride, octadecyl trimethyl ammonium chloride, polyethyleneglycol lauryl ether, polyethylene esters of fatty acids and rosin acids,e.g., Ethofat 7 and 13, sodium N-methyl-N-oleyltaurate, Turkey red oil,sodium dibutylnaphthalene sulfonate, sodium lignin sulfonate (MarasperseN), polyethylene glycol stearate, sodium dodecylbenzene sulfonate,tertiary dodecyl polyethylene glycol thioether (Nonionic 218), longchain ethylene oxidepropylene oxide condensation products, e.g.,Pluronic 61 (molecular weight 1000), sor- 8 bitan sesquioleate,polyethylene glycol ester of tall oil acids, sodium octylphenoxyethoxyethyl sulfate, tris (polyoxyethylene) sorbitan monostearate(Tween sodium dihexyl sulfosuccinate.

The solid and liquid formulations can be prepared by any of theconventional procedures. Thus, the active ingredient can be mixed withthe solid carrier in finely divided form in amounts small enough topreserve the free-flowing property of the final dust composition.

In the following examples or tables illustrating nematocidal andfungicidal activity the phosphorus-containing disulfides were formulatedas wettable powders consisting of 50% of the phosphorus-containingdisulfide, 46% ultra fine silica (Hi-Sil), 2% sodium lignin sulfonateand 2% Pluronic L-61 (polyethylene oxide-propylene oxide adduct,molecular weight about 1000). This wettable powder is hereinafterdesignated as Formulation A.

Formulation A was diluted with water to such an extent to give the finalconcentrations of the phosphoruscontaining disulfide indicated in Tablel.

The saprophytic nematode tests recorded in Table 1 were carried out inwater as the medium with Panagrellus and Rhabditis spp. at roomtemperature. The results were recorded as percent kill after a 2-dayincubation period. The blank mortality was a 5-10% kill.

Table 1 Percent Kill of Nematodes at Rates, ppm. Compound 100 100 S0 5050 10 100 100 100 30 10 10 100 S0 100 100 T0 70 70 (50 40 40 40 1O 1O 1010 10 From the above test, it can be seen that the lower alkyl analoguespossess superior activity to the phenyl analogue in the polyhalovinylseries. Also, the lower alkyl polyhalovinyl compounds were considerablysuperior to the corresponding trihaloethyl compounds.

In commercial practice the compositions containing the nematocides ofthe present invention are applied to the soil infested with nematodes.

The compounds were also tested as fungicides in plate fungicide testsagainst Pythium spp. and Rhizoctonia as shown in Table 2. The compoundswere made up into Formulation A and then added to agar cultures of thefungi. In the table, 10 indicates 100% effectiveness and 0 indicates noeffectiveness. The concentrations are expressed as ppm. (parts permillion).

Bactericide tests were run by incorporating the compounds in FormulationA and adding this mixture to an agar culture of the bacteria.Dimethyl-thiophosphoryl- (2,2-dichlorovinyl) disulfide anddiethyl-thiophosphoryl- (2,2-dichloroviny1) disulfide showed activity at1000 p.p.m. against Xanthomonas vesicatoriar.

I claim:

1. A compound having the formula Where R is selected from the groupconsisting of lower alkyl, phenyl, lower alkylphenyl, and halophenyl, YY and Y are selected from the group consisting of hydrogen and halogenwith at least two of Y Y and Y being halogen, X is a halogen of atomicweight between 16 and 32 and all halogen atoms of said compound have anatomic weight between 35 and 80.

2. Di lower alkyl thiophosphoryl (polychlorovinyl) disulfide.

3. A compound according to claim 2 wherein the lower alkyl groups have 1to 2 carbon atoms.

4. A compound according to claim 3 wherein the polychlorovinyl group has2 chlorine atoms.

5. Dimethyl thiophosphoryl-(2,2-dichlorovinyl) disulfide.

6. Diethyl-thiophosphoryl (2,2 dichlorovinyl) disulfide.

7. Dimethyl thiophosphoryl-(1,2-dichlorovinyl) disulfide.

8. Diethyl-thiophosphoryl (1,2 dichlorovinyl) disulfide.

9. Di lower alkyl phosphoryl (polychlorovinyl) disulfide.

10. A compound according to claim 9 wherein the lower alkyl groups have1 to 2 carbon atoms.

11. A compound according to claim 10 wherein the polychlorovinyl grouphas 2 chlorine atoms.

12. Diethyl phosphoryl (2,2 dichlorovinyl) disulfide.

13. Di lower alkyl phosphoryl-(2,2-dichlorovinyl) disulfide having 1 to2 carbon atoms in the alkyl groups.

14. A process of killing nematodes comprising subjecting the nematodesto a nematocidally effective amount of a compound having a formulaselected from the group consisting of where R is selected from the groupconsisting of lower alkyl, phenyl, lower alkylphenyl, and halophenyl, Ris lower alkyl, Y Y and Y are selected from the group consisting ofhydrogen and halogen with at least two of Y Y and Y being halogen and Y,is halogen, X is a chalcogen of atomic weight between 16 and 32 and allhalogen atoms of said compound have an atomic weight between 35 and 80.

15. A process of killing nematodes comprising subjecting the nematodesto a nematocidally effective amount of di lower alkyl thiophosphoryl(polychlorovinyl) disulfide.

16. A process according to claim 15 wherein the alkyl groups have 1 to 2carbon atoms and the polychlorovinyl group has 2 chlorine atoms.

17. A process of killing nematodes comprising subjecting the nematodesto a nematocidally elfective amount of di lower alkyl phosphoryl(polychlorovinyl) disulfide.

18. A process according to claim 17 wherein the alkyl groups have 1 to 2carbon atoms and the polychlorovinyl group has 2 chlorine atoms.

19. A process of killing fungi comprising subjecting said fungi to afungicidally effective amount of a compound of claim 1.

20. A process of killing fungi comprising subjecting said fungi to afungicidally effective amount of di lower alkyl thiophosphoryl(polychlorovinyl) disulfide.

21. A process according to claim 20 wherein the alkyl groups have 1 to 2carbon atoms and the polychlorovinyl group has 2 chlorine atoms.

22. A process of killing fungi comprising subjecting said fungi to afungicidally efiective amount of di lower alkyl phosphoryl(polychlorovinyl) disulfide.

References Cited in the file of this patent UNITED STATES PATENTS

1. A COMPOUND HAVING THE FORMULA
 14. A PROCESS OF KILLING NEMATODESCOMPRISING SUBJECTING THE NEMATODES TO A NEMATOCIDALLY EFFECTIVE AMOUNTOF A COMPOUND HAVING A FORMULA SELECTED FROM THE GROUP CONSISTING OF